Vat dyestuffs



Patented Jan. 14,' 1941 UNITED STATES PATENT OFFICE va'r nmsrvrrs Ernst Honold and Max Schubert, Frankfort-onthe-Main-Fechenheim, Germany,

mignorlto General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application September 14, 193i. N0. 163,748. In GEM September 16,

'4 Claims. (Cl. 260-205) This invention relates to vat dyestuii's, more I particularly to those .of the general'i'ormula wherein X, X1, A and n have the above signification, or their functional derivatives. with amines of vattable ring systems. The carboxylic acid derivatives employed may. contain any further substituents in their molecule, especially further azo and azoxy groups, and the amines of vattable ring systems used as second condensation component may also contain further substituents.

The new dyestufis'thus obtained dye vegetable fibers from the vat various shades oi good fastness to chlorine and boiling and in many casesv of excellent fastness to light. v i

It is a" surprising fact that the new dyestufis can be vetted by means of the usual-reducing agents without splitting off the molecule by free ducing the azo or azoxy groups which are present in the molecule.

In order to further illustrate our invention the following examples are given, the pants being by weight and all temperatures in degrees centi-v radef but we wish it, howevento be understood that our invention is not limited to the examples iven nor to the exact conditions stated therein.

1 Example 1 27 parts of azobenzene-4.4-dicarboxylio acid are converted into the corresponding acid dichloride by means of 30 parts of thionylchloride in the presence of about 200 parts of o-dichlorobenzene. Then theexcess of thionyl chloride is distilled oi. the remaining solution of the azobenzene-4A'-dicarboXyllc acid dichloride is mixed at about 160 with the solution 01' 45 parts of 01' 1- aminoa thraquinone-in about 400 parts of o-dichlorobenz ne and the mixture is; heated to b iling for about 3hours in'an apparatus provided with a reflux condenser. The condensation Product formed of the, formula:

zirecipitates already while hot. It is a hardly soluble yellow powder which is filtered off and washed. Thenew dyestuii thus obtained is soluble in concentrated sulfuric acid with a brownorange color and dyes cotton from a red vat fast greenish yellow shades.

' Example 2 27 parts of azobenzene-4.4'-dicarboxylic acid are converted into the corresponding acid dichloride as described inExample l. The acid dichloride obtained is condensed with '70 parts of 1- amino-S-benzoylaininoanthraquinone. The cone densation product iormed of the formula:

dissolves in concentrated sulfuric acid with an orange-brown color and dyes cotton from a dark red vat very fast yellow shades, especially of ex cellent fastness to light and weather.

Example 3 By employing l-amino-4-benzoylaminoanthraquinone instead of 1-amino-5-benzoylaminoanthraquinone in Example 2 a condensation product of the formula:

is obtained which dissolves in concentrated sulfuric acid with a brown-red color. It dyes cotton from a violet vat orange-red shades of very good fastness to light and chlorine.

Example 4 29 parts of azoxybenzene-4A'-dicarboxylic acid are converted into the corresponding acid dichloride by boiling with 30 parts of thionyl chloride in about 200 parts of o-dichlorobenzene. Then the excess of thionyl chloride is distilled oil, the remaining solution of the azoxybenzene-4A' dicarboxylic acid dichloride is mixed at about -180 with a solution of 70 parts of 1-amino- 5-benzoylamino anthraquinone and the mixture is'heated to boiling for some hours inan apparatus provided with a reflux condenser. The condensation product formed of the formula:

is filtered ofi and washed. It is soluble in concentrated sulfuric acid with an orange-red color and dyes cotton from a dark red vat very fast yellow shades which are identical with those obtained with the dyestufi prepared according to Example 2.

Example 5 When azobenzene-3.3'-dicarboxy1ic acid or chloride is condensed .with l-arnino-S-benzoylaminoanthraquinone according to the method described in Example 2. a mm 18 obtained of the formula:

It is soluble in concentrated sulfuric acid with a brown color and dyes cotton from a dark red vat fast yellow shades.

Examples 25 parts of 5-aminoanthrapyrimidine are condensed with 16 parts of azobenzene-4.4'-dicarboxylic acid dichloride by heating the two condensation components in o-dichlorobenzene to about -200 for some hours while stirring. The condensation product formed of the formula:

is filtered ofl. while hot and washed. It is soluble in concentrated sulfuric acid with an orangebrown color and dyes cotton from a dark red vat fast yellow shades.

By employing 4-aminoanthrapyrimidine instead rof 5-aminoanthrapyrimidine a similar vat dyestufl is obtained which yields more greenish yellow shades.

Example 7 37 parts of 4-amino-l,2-(2'-chlorophenyl-imidamle) -anthraquinone of the formula:

I NH:

are condensed with 16 parts of azobenzene-4.4'- dicarboxylic acid dichloride by heating the two components in o-dichlorobenzene to boiling for a me hours. The condensation product formed a! the formula:

is soluble in concentrated sulfuric acid with a yellow-orange color and dyes cotton from a red vat yellow-orange shades of excellent Iastness properties.

Example 8 25 parts or l-anrino-B-benzoylaminoanthraquinone are finely divided and condensed with 31 parts of azobenzene-qLQ-dlcarboxylic acid dichloride in the presence of parts of pyridine by stirring at about 40-50 for some hours. Then the mass is added to a solution of 35 parts of 1- amino-4-benzoylaminoanthraquinone in o-dichlorobenzene at about 160 and the mixture is heated to about 180 for 3 hours while stirring. The dyestufl iormed of the formula:

precipitates while 'hot. It dyes cotton from a red-violet vat orange shades of valuable i'astness properties.

By employing 25 parts of 1-aminoanthraquinone instead of the 35 parts 01. l-amino--benzoylaminoanthraquinone in the above example a similar vat dyestufi is obtained which yields fast'yellow shades.

Example 9 9 parts of the condensation product of the formula:

' (confer 1. S. Patent No. 1,850,562) are finely divided in nitrobenzene and condensed with 3.5

parts of azobenzene-4.4'-dicarboxylic acid dihours. The condensation product formed of the formula 2 is soluble in concentrated sulfuric acid with an olive-green color and dyes cotton from a violetblue vat very fast khaki shades. I

By employing the amines 01 further vattable ring systems such as for example amines or diamines oi. the dibenzanthrone or anthanthrone series as condensation components, similar valuable vat dyestuffs are obtained.

Example 10 33 parts of 3.3'-dimethoxyazobenzene-4.4'- dicarboxylic acid (prepared by alkaline reduction of 2-methoxy-4-nitrobenzoic acid) are converted into the corresponding acid dichloride according to the method described in Example 1 by means of thionyl chloride in the presence 01 o-dichloro-benzene. The 3.3-dimethoxyazobenzene-4..4'-dicarboxylic acid dichloride obtained is condensed with 70 parts oi'1-amino-5-benzoy1- aminoanthraquinone. The condensation product formed of the formula:

chloride by stirring at about 200-220 for some is soluble in concentrated sulfuric acid with a dark red color and dyes cotton from a red-violet vat very fast yellow shades.

Example 11 NH-O c-C) mo 001m;

CO-NH o NH-C o0 is soluble in concentrated sulfuric acid with an orange color and dyes cotton from a red-violet vat very fast yellow shades.

Example 12 37 parts of azobenzene-4,3',5'-tricarboxylic acid trichloride of 135 melting point are added to a solution of 67 parts of l-aminoanthraquinone in about 700 parts of o-dichlorobenzene at about 160 and the mixture is stirred at this temperature for about 2 hours. Then the dyestuif formed of the formula:

which is gbtalned with a very good yield, is filtered ofi, washed and dried. It is soluble in concentrated sulfuric acid with an orange-brown color and dyes cotton from a violet-red vat very fast greenish yellow shades.

The azobenzene-{Lii',5'-tricarboxylic acid trichloride employed may be prepared for example by condensing the methylester of p-nitroso-benzoic acid with 5-amino-isophthalic acid in glacial acetic acid, saponifying the methylester group of the condensation product obtained in an alkaline medium and converting the tricarboxylic acid formed into the corresponding. acid trichloride by means of phosphorus pentachloride in monochlorobenzene.

Example 13 N-oo (JO-NH HN-O ONH is filtered oil when cool, washed and dried. It is soluble in concentrated sulfuric acid with an orange-brown color and dyes cotton from a dark red vat very fast greenish yellow shades.

The azobenzene-3,5,3',5'-tetracarboxylic acid tetrachloride employed may be prepared for example by reducing 5-nitro-isophthalic acid in an alkaline 'medium and converting the tetracarboxylic acid obtained into the corresponding acid tetrachloride by means of phosphorus pentachloride.

A dyestuff which yields dyeings identical with those of the above dyestufl is obtained by employing azoxybenzene-3,5,3',5'-tetracarboxylic acid tetrachloride instead of azobenzene-3,5,3',5'- tetracarboxylic acid tetrachloride. The azoxybenzene-3,5,3',5-tetracarboxylic acid may be prepared for example by reducing 5-nitroisophthalic acid by means of sodium arsenite in an alkaline medium according to the method of Loesner (confer Journal fiir praktische Chemie, vol. 50, page 365).

Example 14 46 parts of diphenylazodiphenyl-4.4'-dicar# boxylic acid dichloride of the formula:

chlorobenzene at about 160 and the mixture is.

stirred at this temperature for about one hour.

Then the condensation product formed of the formula:

is filtered ofi, washed and dried. It is soluble in concentrated sulfuric acid with a brownish-red color and dyes cotton from aviolet vat very fast yellow shades. t

The diphehylazodiphenyl-4A-dicarboxylic acid dichloride employed for this example crystallizes in red needles of 250 melting point. It maybe prepared for example by reducing 4-nitrod1- phenyl-4'-carboxylic acid by means of grape sugar and converting the diphenylazodiphenyl- 4,4'-dlcarboxylic acid obtained into the correo ii o sulfuric acid th a dark red color and dyes cot-, ton from a violet vat valuable orange shades.

' Example 16,

24 parts of diphenylazoxydiphenyi4,4-dicarboxylic acid dichloride are slowly added to a solution of 35 parts of 1-amino-5-benzoylami- 'noanthraquinone in about 500 parts of monochlorobenzene at about IOU-120 and the mixture is heated to boiling for about 1 hour while stirring in an apparatus provided with a reflux condenser. Then the dyestufi formed of the formula:

sponding acid dichloride by means of phosphorus pentachloride.

By employing instead of l-aminoanthraquinone the corresponding amount of 1-amino-6- chloroanthraquinone as condensation component, a very similar vat dyestufl of likewise valuable fastness properties is obtained.

Example By condensing 46 parts of diphenylazodiphenyl- 4,4'-dicarbo1 ylic acid dichloride with 69 parts of 1-amino-5-benzoylaminoanthraquinone according to the method described in Example 14, a vat dyestufl is obtained of the formula:

which is soluble in concentrated sulfuric acid with a red color. It dyes cotton trom a violet vat yellow shades of excellent fastness properties.

By employing instead of 1-amino-5-benzoylaminoantpraquinone the same amount of 1- amino-4-benzoylaminoanthraquinone, a vat dyestuff is obtained which dissolves inlconce'ntrated Example 17 49 parts of diphenyleneoxide-azo-diphenyleneoxide-2,2'-dicarboxylic acid dichloride of the formula:

are slowly added to a solution of 70 parts of ,1- amino-5-benaoylaminoanthraquinone in about 700 parts of o-chlorotoluene at about 140 and the mixture is heated to boiling forabout 4 hours in an apparatus provided with a reflux condenser. Then the dyestufl formed of the formula: 1

boxylic acid dichloride of 215 melting point are added to a solution of 35 parts or 1-amino-5- benzoylaminoanthraquinone in about 400 parts of 5 01-0 oQQm Q-Qc 0-01 is filtered off. washed and dried. It is soluble in concentrated sulfuric acid with a violettishred color and dyes cotton from a violet vat very fast orange-yellow shades.

By employing 1- amino-4-benzoylaminoanthraquinone as condensation component a similar dyestuff is obtained. l-aminoanthraquinone used as condensation component yields a vat dyestuff which dies cotton valuable yellow shades.

The 2,2-dicarboxylic acid dichloride employed may be prepared for example by reducing 7'-nitrodiphenyleneoxide-2-carboxylic acid by means of grape sugar and sodium hydroxide solution, and converting the diphenyleneoxide-azo-diphenylene-oxide-2,2'-dicarboxylic acid obtained into the corresponding acid dichloride by means oi! thionyl chloride. 7 -nitrodiphenyleneozdde-Z-carboxylio acid is prepared for example by nitrating diphenyleneoxide in a glaciaLacetic acid solution, condensing the nitro compound obtained with acetyl chloride and aluminiumchloride and oxidizing the aceto compound formed with an alkaline chlorine solution. v

Similar valuable vat dyestufis are obtained by employing instead of diphenyleneoxide-azo-di phenyleneoxide-dicarboxylic acid dichloride corresponding derivatives of the fluorene, carbazole and diphenylenesulfide series, such for example as the compounds corresponding to the following formulae: I

diphenyleneoxide-azo-diphcnyleneoxide trichlorobenzene at about 160-180. The condensation product formed of the formula:

precipitates from the solution while hot after a short time. It is filtered oil, washed and dried. The new dyestufl thus obtained is soluble in concentrated sulfuric acid with a brownish red color and dyes cotton from a red-violet vat very fast reddish yellow shades.

The l,1'-azonaphthalene-5,5'-dicarboxylic acid dichloride employed may be prepared for example by reducing -nitronaphthalene-1-carbox ylic acid by means of grape sugar in an alkaline medium, and converting the sodium salt of the 1,1-azonaphthalene-5,5-dicarboxylic acid obtained into the corresponding acid dichloride by means of thionyl chloride.

Example 19 29 parts of the dicarboxylic acid dichloride of the formula:

c1-o cQ-fcgn 0 03190 oo1 Example 18 are condensed with 70 parts of 1-amino-5-ben- 75 20 parts of 1,1'-azonaphthalene-5,5'-dicar-' zoylaminoanthraquinone by boiling the two components in o-dichlorobenzene for some hours. The dyestufl formed of the formula:

is soluble in concentrated sulfuric acid with an orange-brown color and dyes cotton from a violet vat greenish yellow shades of valuable fastness properties.

The dicarboxylic acid dichloride employed of the above formula crystallizes from o-dichlorobenzene in yellow needles melting above 300. It may be prepared for example by reducing 2-(4'- nitrophenyl)-benzthiazole-6-carboxylic acid byv means of grape sugar and converting the dicarboxylic acid obtained into the corresponding acid dichloride by means of phosphorus pentachloride.

Example 20 48 parts of amino-dibenzanthrmie are finely divided in about 600 parts of trichloro-benzene and the suspension is stirred at about 180. Then 18 parts of 3,3-azocinnamic acid dichloride of theformula:

01-0 CHC=CHI cH=cH-o oc1 are added and the mixture is stirred for about 3 hours at about 100. The condensation product formed of the formula:

is filtered off while hot, washed and dried. It is soluble in concentrated sulfuric acid with a dark brown-red color and dyes cotton from a blue vat blue shades.

Example 21 18 parts of 4,4-azocinnamic acid dichloride of the formula:

01-0 o-nomcO-xvmOcmcK-c 0-01 are added to a solution of 35 parts of 1-amino-5- benzoylamino-anthraquinone in about 400 parts of monochlorobenzene and the-mixture is heated to boiling for about 2-3 hours in an apparatus formed of the formula:

provided with a reflux condenser. The dyestuff formed of the formula:

0 o-mn precipitates already while hot and is filtered oil, washed and dried. It dissolves in concentrated sulfuric acid with a red-brown color and dyes cotton froni'a violet vat orange shades of excellent fastness properties.

The 4,4'-azocinnamic acid dichloride employed J-crystallizes from benzene in yellow needles of 221 melting point.' It may beprepared for ex ample by reducin 4-nitrocinnamic acid by means of grape sugar in an alkaline solution and convetting the 4,4-azocinnamic acid obtained into the corresponding acid dichloride by means of thionyl chloride in a monochlorobenzene solut on. 1

Example 22 18 parts of 4,4'-azophenoxyacetic acid dichloride of the formula:

are condensed with 35 parts of 1-amino-5-benzoylaminoanthraquinone by heating the two components in o-dichlorobenzene at about 160- 180 for some hours. The condensation product V 0 o HN-OC O-c O-NH is filtered oil when cool. It dissolves in concentrated sulfuric acid with an orange color and dyes cotton from a violettish red vat fast greenish yellow shades.

The 4,4-azophenoxyacetic-acid dichloride. employed for this example crystallizes from benzlne in flesh-colored needles of- 125 melting point. It may be prepared for example by. reducing 4-nitrophenoxyacetic acid by means of grape sugar in an alkaline solution and converting the 4,4'-azophenoxyacetic acid obtained into the corresponding acid dichloride by means of thionyl chloride in a monochlorobenzene solution.

Ezample 23 15 parts of 4,4-azophenylacetic acid of the formula:

are boiledwith an excess of thionylvchloride in o-dichlorobenzene, until the substance is wholly dissolved. Then the excess of thionyl chloride is distilled ofi, the remaining solution of the 4A- azophenylacetic acid dichloride formed is added to a solution of 35 parts of I-amino-S-benzoylaminoanthraquinone in about 400 parts of o-dichlorobenzene at about 160? and the mixture is heated to this temperature for about 2 hours.

The condensation product formed of the formula:

color and dyes cotton from a dark red vat fast yellow shades.

Example 24 By condensing 1 molecular weight of benzicline with 2 molecular weights of the methyl ester of 4-nitrosobenzoic acid, saponifying the condensation product formed and treating it with phosphorus pentachloride, a dicarboxylic acid dichloride is obtained which crystallizes in orange-yellow prisms of 235 melting point and corresponds to the formula:

48 parts of this compound are slowly added while stirring at about 160 to a solution of 45 parts of l-amlnoanthraquinone in about 500 parts of o-dichlorobenzene. The mixture is stirred for about 2 hours at about 200 and the condensation product formed of the formula:

is filtered off when cool. It is soluble in concentrated sulfuric acid with a red-violet color and dyes cotton from a dark red-violet vat yel-low shades of excellent fastness properties.

Example 25 By condensing 1' molecular weight of 4,4-diamino-azo-benzene with 2 molecular weights of the methyl ester of 4-nitroso-benzoic acid, saponifying the condensation product formed and treating it with phosphorus pentachloride, a dicarboxylic acid dichloride is obtained which crystallizes from monochlorobenzene in orangeyellow lamellae melting above 300 and corresponds to the formula:

is filtered off at about 100, washed and dried. It is soluble in concentrated sulfuric acid with a red-violet color and dyes cotton from a violet vat orange-yellow shades of very good fastness properties.

Example 26 By condensing 1 molecular weight of 4,4'-diamino-benzophenone with 2 molecular weights of the rnethyl ester of 4-nitrosobenzoic acid, saponifyins the condensation product obtained and treating it with phosphorus pentachloride, a di-carboxylic acid dichloride is obtained which crystallizes from monochlorobenzene in fleshcolored needles of 242 melting point and corresponds to the formula;

51 parts of this compound are condensed with 69 .parts of 1-amino-5-benzoylaminoanthraquinone according to the method described in 'Example 25. The condensation product formed of the formula:

210 @fO -Ow I NH Iii-0 o-O O0 O-NH is soluble in concentrated sulfuric acid with a R brown-orange color and dyes cotton from a violet vat reddish yellow shades of excellent-fastness properties.

By starting from the dicarboxylic acid dichloride of the corresponding azoxy compound which is obtainable for example from the above amcompound by oxidation with hydrogen peroxide,

a yellow vat dyestufi is obtained dyeing cotton from the vat reddish yellow shades which are identical with those obtained by means of the above dyestufi. Similar vat dyestuffs are obtained by employing the methyl ester of 3-nitrosobenzoic acid instead of the methyl ester of 4- nitrosobenzoic acid for the manufacture of the dicarboxylic acid dichloride used as condensation component.

Example 27 By condensing 1 molecular weight of 4,4',4"- triamino-triphenylmethane with 3 molecular weights of the methyl ester of 4.-nitrosobenzoic acid, saponifying the condensation product ch- 51 parts of this compound are condensed-with 69 parts of l-amino-5-benzoylaminoanthraquinone in about 700 parts of o-dichloro-benzene according to the method described in Example 24. The condensation product formed of the formula:

HN 0 0 NH HN-O 00 Q --o O-NH tained and treating it with phosphor-us .pentachloride, a tricarboxylic acid .trichloride is obtained which crystallizes from benzine in orange needles of 215 melting point and corresponds to the formula:

1 molecular weight of this compound is condensed with 3 molecular weights of 1-amino-5- benzoylaminoanthraquinone according to the method described in Example 25. The condensation product formed of the formula:

is soluble in concentrated sulfuric acid with a brown color and dyes cotton from a violet vat orange-yellow shades of very good fastness properties.

We claim:

1. The vat dyestuffs of the general formula:

wherein X and X1 stand for members selected from the group consisting of the radicles of the benzene, naphthalene, diphenyl, fluorine, diphenylene oxide, diphenylene sulfide, carbazole and benzthiazole series, A stands for a member selected from the group consisting of the azo and azoxy group, R1 stands for a radicle of a vattable ring system containing an anthraquinone radicle and n stands for one of the numbers 2 to 4, which dyestuffs dye vegetable fibers from the vat various shades of good fastness to chlorine and boiling and in many cases of excellent fastness to light.

2. The vat dyestufl of the formula:

which dyestuff is soluble in concentrated sulfuric acid with an orange-brown color and dyes cotton from a dark red vat very fast yellow shades, especially of an excellent fastness to light and weather.

3. The vat dyestufl' of the formula:

which dyestuff is soluble in concentrated sulfuric acid with an orange-brown color and dyes cotton from a dark red vat very fast greenish yellow shades.

4. The vat dyestufi of the formula:

HN--0 0-0-0- =N-O-O-CO-NH o o NH-O 0-0 0-0 0- n which dyestufl is soluble in concentrated sulfuric acid with a red color and dyes cotton from a violet vat yellow shades of excellent fastness properties. 7

ERNST HONOLD. MAX 

